Method for making metal-to-ceramic seals

ABSTRACT

An alkali metal corrosion resistant vacuum tight metal-toceramic seal is formed between a high alumina ceramic body and a refractory alkali metal resistant metal member, such as Cb-1Zr, by interposing a powdered brazing mixture comprising by weight a majority of elemental columbium powder and a second metal powder selected from the class consisting of iron and nickel, and firing the assembly in vacuum at a temperature between 1,500*C and 1,675*C to partially melt a portion of the powder to form a melted bonding phase component interstitially of the undissolved columbium particles for bonding the ceramic to the metal part.

United States Patent 1 Anderson [4 1 June 5, 1973 54] METHOD FOR MAKING METAL-TO- 3,594,895 7/1971 Hill ..29/473.1

CERAMIC SEALS Primary Examiner-John F Campbell [75] Inventor. ggfirtnan C.-Anderson, Foster City, Assistant Examiner Ronald 1. Shore Attorney-Stanley Z. Cole [73] Assignee: Varian Associates, Palo Alto, Calif. 22 Filed: June 1,1971 [57] ABSTRACT An alkali metal corrosion resistant vacuum tight [2}] Appl' 148891 metal-to-ceramic seal is formed between a high alumina ceramic body and a refractory alkali metal re- [52] [1.8. Cl ..29/473..l sistant metal member, such as Cb-IZr, by inter-posing [5]] Int. Cl. ..B23k 31/02 a powdered brazing mixture comprising by weight a [58] Field of Search ..29/473.l, 504; majority of lemental columbium powder and a 134 R second metal powder selected from the class consisting of iron and nickel, and firing the assembly in e n e Cited 7 vacuum at a temperature between 1,500C and 1,675C to partially melt a portion of the powder to UNITED STATES PATENTS form a melted bonding phase component interstitially 3,376,121 4/1968 Lawrence ..29/473.1X of the undissolved columbium particles for bonding 3,386,160 6/1968 Mitch et al. ..29/473.1 the ceramic to the metal part. 3,389,215 6/1968 Rice et al.... 287/l89.365 X 3,479,170 11/1969 Louden ..29/473.l X

13 Claims, No Drawings METHOD FOR MAKING METAL-TO-CERAMIC SEALS GOVERNMENT CONTRACT The invention herein described was made under a contract with the U.S. Navy.

DESCRIPTION OF THE PRIOR ART Heretofore, attempts have been made to make vacuum tight, high strength, brazed seals between a high alumina body and an alkali corrosion resistant metal member, as of Cb-lZr. In this prior art, a high temperature brazing alloy, Cb-33Fe, foil was placed between the metal member and a bare or tungsten metalized ceramic member to be brazed. The assembly was heated in vacuum to a brazing temperature of approximately l670C for melting the brazing alloy and forming a brazed joint between the Cb-lZr member and the high alumina body.

The resultant metal-to-ceramic joints were relatively weak, especially with bare ceramic, thereby making such metal-to-ceramic seals unsuited for high temperature high strength applications as. required for use in thermionic energy converters and high power infrared radiation sources, such as pulsed cesium. vapor arc lamps. The aforecited Cb-33Fe brazement alloy and seal configuration is disclosed in the final technical report on U.S. Navy contract NObs-90496, titled Research and Development Program of Thermionic Conversion Of Heat To Electricity, by General Electric Nuclear Therrnionic Power Operation, Pleasanton, California, Volume 2, July, I968.

SUMMARY OF THE PRESENT INVENTION The principal object of the present invention is the provision of an improved method for making metal-toceramic seals.

In one feature of the present invention, the ceramic body is coated with abrazing mixture which includes a volatile vehicle in which is suspended a powdered mixture comprising by weight a majority of columbium powder and a second metal powder selected from a class consisting of iron and nickel. The coated ceramic body is fired in vacuum with an assembled metal mem ber to a temperature sufficiently high to produce'a partial melting of the powdered mixture such that upon cooling a solidified bonding phase component is formed interstitially of the undissolved columbium particles for bonding the columbium particles to the ceramic body, whereby a high strength bond between the columbium particles and the ceramic body is obtained.

In another feature of the present invention, the ceramic body is selected from the class consisting of alumina, pore free translucent alumina, and sapphire.

In another feature of the present invention, a metal part which is to be bonded to the ceramic is selected from the class consisting of tantalum, tantalum alloys, molybdenum, columbium, and columbium alloys.

Other features and advantages of the present invention will become apparent upon a perusal of the following specification.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A brazing mixture is prepared which comprises a powdered mixture of metal powders suspended in a volatile vehicle. The powdered mixture is formulated by combining appropriate amounts of -325 mesh elemental columbium powder and 325 mesh iron powder or l00 mesh nickel powder. The powders are combined with a majority of columbium powder by weight. More particularly, a preferred embodiment employs approximately 17 percent iron powder or in the case of nickel, approximately 15 percent by weight nickel powder.

The powders are mixed with a Lucite based lacquer, such as butyl methacrylate, to give the desired consistency. The solid and liquid constituents of the brazing mixture are mixed by holding them in a rolling container, either with or without a grinding media, for several hours. This serves to intimately mix the metal powders and to promote their suspension in the liquid media.

The brazing mixture is applied to that region of a ceramic body to be sealed. Suitable ceramic bodies include high alumina ceramic, (where high alumina" is defined to mean percent or more of A1 0 pore free translucent alumina, and sapphire. The brazing mixture may be applied by any suitable means, such as by needle painting, roller coating, brushing, dipping, or

spraying. The coating is preferably applied to a thickness, as of 0.005 to 0.010 inch.

The coated ceramic bodies to be brazed are assembled'with the metal member, to be joined to the ceramic, in a molybdenum or molybdenum-alumina brazing fixture and allowed to dry for several hours. Tungsten of molybdenum weights are used so that the seal area is under a minimum axial compressive load, as of 0.6 pounds per square inch.

As an alternative to applying the brazing mixture directly to the ceramic body, a first metalizing layer may be applied and sinter-fired onto the ceramic body and the brazing mixture subsequently applied to the metalized layer. Suitable metalizing metal layers include molybdenum and tungsten. Such underlaying metalized layers may be applied to the ceramic body as by evaporation in vacuum or by sputtering, in a glow discharge at relatively low pressure, as of ll) torr. More commonly such layers can be applied in the form of metalizing paints and subsequently sinter-iired at high temperature to achieve a dense adherent coating.

The ceramic, metalized or bare, and metal assembly is fired in vacuum to a brazing temperature sufficiently high to produce only a partial melting of the powdered mixture, such that upon cooling a solidified bonding phase component is formed interstitially of the dissolved'columbium particles for bonding the undissolved columbium to the ceramic body; The undissolved columbium particles form a ductile metal bridge between the ceramic body and the metal part. The lacquer vehicle volatilizes at low temperature and is pumped by the vacuum system. A suitable brazing temperature range is between 1500C and 1675C.

The resultant metal-to-ceramic seals are vacuum tight, have relatively strong tensile strength, as of 20,000 psi, and are corrosion resistant to alkali metal. The joints may be repetitively cycled to relatively high temperatures, as of l,000C or higher, in continuous exposure to alkali metal liquid or vapor.

Formationof the final brazement configuration from an initial Cb-l7Fe mixture probably occurs as follows: During heatup, the first liquid appears at 1370"C corresponding to the CbFe -Fe (solid solution) eutectic. As temperature is increased to 1600C, additional columbium dissolves in the melt until the melt composition corresponds to the Cb Fe -cbFe eutectic point. A considerable amount of undissolved particulate columbium remains, and at this point, a kind of pseudoequilibrium is reached because further dissolution of columbium tends to freeze the melt phase.

Quantitative electron probe microanalysis of the particulate and continuous regions in Cb-17Fe brazements confirms the above description. Compositions of the respective regions were found to be Cb-8%Fe and Ch- 34%Fe by weight. Evidently, the undissolved columbium particles are saturated with iron by solid state diffusion during the brazing process.

The Cb-l7Fe brazement can be thought to consist of columbium-rich particles that form a bridge-like network between the Cb-lZr and pore free translucent alumina (Lucalox) members, and a hard, continuous cementing or bonding phase that provides the essential bonding. The columbium rich particulate phase probably matches the Lucalox ceramic member quite well in thermal expansion behavior owing to the positive influence of the undissolved iron.

The cementing or bonding phase, actually a two phase Cb Fe CbFe eutectic micromixture, is expected to have a somewhat higher thermal expansion coefficient than the alumina body. Ordinarily, a mismatch of this sort, coupled with the high elastic moduli of the ceramic and cementing phase, would impart high shearing stress to the ceramic-brazement interface. The presence of the large volume fraction of columbiumrich particulate phase in the brazement conceivably mechanically constrains the cementing phase to follow an average thermal expansion (or contraction) path determined by the weighted contributions of the phases present (with the weightings being based primarily on respective volume fractions and elastic moduli). Thus, the average thermal expansion behavior of the brazement composite probably is not very much different from that of the Lucalox and, consequently, interfacial stresses-are probably low.

In the case where nickel powder is mixed with columbium powder, a particularly suitable mixture is CblSNi. When such mixtures are brazed at temperatures above l500C, bond strengths are obtained which are comparable to those obtained with the aforedescribed Cb-l7Fe brazements. The resultant brazement is quite similar in structure to the Cb-Fe structure. More particularly, a particulate phase of undissolved columbium is obtained with a continuous or cementing phase of CbNi interstitially disposed of the undissolved columbium particles and forming a thin bonding layer between the particulate columbium and the underlaying ceramic body.

What is claimed is:

1. In a method for making a brazed joint between a ceramic body and a metal member which is resistant to alkali metal corrosion the steps of, coating said ceramic body with a powdered mixture consisting essentially of by weight a majority of columbium powder and a second metal powder selected from the class consisting of iron and nickel, positioning the metal memberin bonding relation with the coated ceramic body. Firing the coated ceramic body in vacuum at a temperature sufficiently high to produce only a partial melting of the powdered mixture such that upon cooling a solidified bonding phase component is formed interstitially of the undissolved columbium particles for bonding the undissolved columbium particles to the ceramic body'and the metal member, whereby the undissolved columbium particles form a ductile metal bridge bonded to the ceramic body and the metal member via the solidified bonding phase component.

2. The method of claim 1 wherein said ceramic body is selected from the class consisting of alumina, pore free translucent alumina, and sapphire.

3. The method of claim 1 wherein the firing temperature range is between l500C and 1675C.

4. The method of claim 1 wherein the second powder comprises iron in the amount of approximately 17 percent by weight of the powdered mixture.

5. The method of claim 1 wherein the second powder comprises nickel in the amount of approximately 15 percent by weight of the powdered mixture.

6. In a method for brazing a metallic member to a ceramic body the steps of, interposing a powdered mixture between the ceramic body and the metal member, said powdered mixture consisting essentially of by weight a majority of columbium powder and a second metal powder selected from the class consisting of iron and nickel, urging the coated ceramic body and metal member into intimate contact with the powdered mixture, and firing the ceramic body, metal member and mixture at a temperature sufficiently high to produce only partial melting of the powder mixture such that upon cooling a solidified bonding phase component is formed interstitially of the undissolved columbium particles for bonding the undissolved columbium particles to the ceramic body and the metal member, whereby the undissolved columbium particles from a ductile metal layer bonded between the metal member and the ceramic body via the solidified bonding phase component.

7. The method of claim 6 wherein the metal member is selected from the cass consisting of class tantalum, tantalum alloys, molybdenum, columbium, and columbium alloys.

8. The method of claim 7 wherein the metal member is Cb-lZr.

9. The method of claim 6 wherein said ceramic body is selected from the class consisting of alumina, pore free translucent alumina, and sapphire.

10. The method of claim 6 wherein the firing temperature range is between l500C and 1675C.

11. The method of claim 6 wherein the second powder comprises iron in the amount of approximately 17 percent weight of the powdered mixture.

12. The method of claim 6 wherein the second powder comprises nickel in the amount of approximately 15 percent by weight of the powdered mixture.

13. The method of claim 1 wherein said ceramic body is metallized with tungsten or molybdenum prior to said step of coating said body with said powdered mixture.

4! l I I I.

@ETTFTCATE OF PATENT NO. ,736,650

DATED 1 June 5, 1973 Q are hereby corrected as shown below:

0 Column 2, lin 9: Change "Lucite" to -methyl methacrylate UNITED STATES PATENT AND TRADEMARK OFFICE INVENTORG) 3 Norman C. Anderson It is certified that erro. appears in the above-identified patent and that said Letters Patent Column 1, line 13: After "alloy" insert --foil-;

After delete "foil".

(Lucite).

Column 2, line 32: Change "pounds" to -pound.

a Column 3, line 62: Change Firing" to and firing--. Column 4 line 37: Change "from" to form Column 4, line 42: Change "cass" to -class-; 5 After "of" delete "class".

Column 4, line 54: After "percent" insert -by Erigned and this J eighteenth Day 0? May 1976 g Arrest:

RUTH C. MASGN C. MARSHALL DANN Q! AHPUMR U/five (ummissium'r ufPalems and Trademark: 

2. The method of claim 1 wherein said ceramic body is selected from the class consisting of alumina, pore free translucent alumina, and sapphire.
 3. The method of claim 1 wherein the firing temperature range is between 1500*C and 1675*C.
 4. The method of claim 1 wherein the second powder comprises iron in the amount of approximately 17 percenT by weight of the powdered mixture.
 5. The method of claim 1 wherein the second powder comprises nickel in the amount of approximately 15 percent by weight of the powdered mixture.
 6. In a method for brazing a metallic member to a ceramic body the steps of, interposing a powdered mixture between the ceramic body and the metal member, said powdered mixture consisting essentially of by weight a majority of columbium powder and a second metal powder selected from the class consisting of iron and nickel, urging the coated ceramic body and metal member into intimate contact with the powdered mixture, and firing the ceramic body, metal member and mixture at a temperature sufficiently high to produce only partial melting of the powder mixture such that upon cooling a solidified bonding phase component is formed interstitially of the undissolved columbium particles for bonding the undissolved columbium particles to the ceramic body and the metal member, whereby the undissolved columbium particles from a ductile metal layer bonded between the metal member and the ceramic body via the solidified bonding phase component.
 7. The method of claim 6 wherein the metal member is selected from the cass consisting of class tantalum, tantalum alloys, molybdenum, columbium, and columbium alloys.
 8. The method of claim 7 wherein the metal member is Cb-1Zr.
 9. The method of claim 6 wherein said ceramic body is selected from the class consisting of alumina, pore free translucent alumina, and sapphire.
 10. The method of claim 6 wherein the firing temperature range is between 1500*C and 1675*C.
 11. The method of claim 6 wherein the second powder comprises iron in the amount of approximately 17 percent weight of the powdered mixture.
 12. The method of claim 6 wherein the second powder comprises nickel in the amount of approximately 15 percent by weight of the powdered mixture.
 13. The method of claim 1 wherein said ceramic body is metallized with tungsten or molybdenum prior to said step of coating said body with said powdered mixture. 